Transition-metal-catalyzed process for the preparation of sterically hindered N-substituted aryloxyamines

ABSTRACT

Sterically hindered N-substituted aryloxyamines are prepared by the transition-metal-catalyzed decomposition of diazonium salts in the presence of a sterically hindered nitroxyl radical. These compounds are useful as thermal and light stabilizers for a variety of organic substrates.

[0001] This application claims benefit under 35 USC 119(e) of U.S.provisional application Serial No. 60/200,988, filed on May 1, 2000.

[0002] This invention pertains to the novel process for preparingsterically hindered N-substituted aryloxyamines by thetransition-metal-catalyzed decomposition of a diazonium salt in thepresence of a sterically hindered nitroxyl radical.

BACKGROUND OF THE INVENTION

[0003] N-Aryloxyamines have been prepared in the prior art by thereaction of a phenylhydrazine with a stable nitroxide. In certaininstances, N-aryloxyamines have been prepared in low yield by thedecomposition of aryldiazonium salts in the presence of a nitroxylradical, but without a transition metal catalyst being present. Thesepapers are often about mechanistic studies with poor yields and statethat the reaction described is limited in scope. A. C. Scott et al., J.Chem. Soc., Perkin Trans. 2, 1980, 260-266.

[0004] In another study, an aryl radical formed from a diazonium saltadded intramolecularly to a double bond and the result alkyl radical wastrapped by a stable nitroxyl radical. L. J. Beckwith and G. F. Meijs, J.Chem. Soc., Chem. Commun. 1981, 595-597.

[0005] In respect to wax stabilization, the use of selected hinderedamines and/or benzotriazole UV absorbers is known in the prior art. Thisis seen in Japanese Hei 3-278554; WO 00/22037; and U.S. Pat. Nos.3,530,084; 4,379,721; 4,616,051 and 5,964,905 and copending applicationsSer. Nos. 09/495,495, 09/495,496 and 09/741,583.

[0006] It is clear that the instant process is a facile and direct wayto prepare these interesting and useful stabilizer compounds in yieldsfar exceeding anything found in the prior art.

DETAILED DISCLOSURE

[0007] The instant invention pertains to a process for preparing asterically hindered N-aryloxyamine of formula I, II, III, IV, V or VI

[0008] which comprises

[0009] reacting a sterically hindered nitroxyl compound of formula VII,VIII, IX, X or XI

[0010] with a diazonium salt of an aromatic amine of formula XII, XIIIor XIV

[0011] in the presence of a transition-metal catalyst

[0012] wherein

[0013] X is —CH₂—, —O—, —S— or —NR₈— where R₈ is hydrogen or alkyl of 1to 12 carbon atoms,

[0014] R₆ and R₇ are independently alkyl of 1 to 8 carbon atoms, or R₆and R₇ together are tetramethylene or pentamethylene,

[0015] E₂ is alkylene of 2 to 12 carbon atoms,

[0016] G is chloro or —N(2-ethylhexyl)₂,

[0017] G₁ is —CH₂—, —CO— or —O—,

[0018] R is hydrogen, alkyl of 1 to 18 carbon atoms, aralkyl of 7 to 15carbon atoms, aryl of 6 to 10 carbon atoms, hydroxyl, carboxyl, amino,alkylamino of 1 to 18 carbon atoms, dialkylamino of 2 to 36 carbonatoms, oxo, alkylthio of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbonatoms, aryloxy of 7 to 15 carbon atoms, benzoyloxy, alkylcarbonyloxy of2 to 18 carbon atoms or alkylcarbonylamino of 2 to 18 carbon atoms, and

[0019] R₁ to R₅ are independently hydrogen, halogen, nitro, cyano, alkylof 1 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to10 carbon atoms, hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms,alkoxy of 1 to 18 carbon atoms, aryloxy of 7 to 15 carbon atoms,alkylcarbonyloxy of 1 to 18 carbon atoms, alkylsulfonyl of 1 to 18carbon atoms, arylsulfonyl of 6 to 15 carbon atoms, sulfo or —P(O)(OH)₂or —P(O)(OR₆)₂, or any two vicinal substituents connected together toform a mono or polycyclic ring, so that formula VII can represent interalia 1-naphthylamine or 2-naphthylamine; or any two vicinal carboxylgroups can be joined to form an imide; or

[0020]  where R, R₆ and R₇ are as defined above.

[0021] The diazonium salt of the aromatic amine of formula VII can beprepared by reaction with an alkyl nitrite ester, such as tert-butylnitrite. The diazonium salt can also be prepared using a nitrite saltand an acid, such as sodium nitrite and hydrochloric acid.

[0022] Indeed, the instant compounds can be made directly fromnitroxides which are commercially available such as TEMPO(1-oxyl-2,2,6,6-tetramethylpiperidine), 4-OXOTEMPO(1-oxyl-2,2,6,6-tetramethyl-4-oxopiperidine) and di-tert-butylnitroxide.

[0023] The reaction is conveniently carried out in acetonitrile assolvent at a temperature of 0 to 100° C., or between 20 and 70° C.

[0024] The transition metal is a metal of Group 4, 5, 6, 7, 8, 9 or 10of the periodic table; for example copper(I), copper(II), cobalt(II),manganese(II), titanium(III), gold(I), iron(II), iron(III), cobalt(II),nickel(II) or chromium(III).

[0025] The process is carried out in the presence of 0.1 mole % tostoichiometric quantities of the transition metal catalyst.

[0026] In another embodiment, the transition metal catalyst is copper(I)or copper (II), for example copper(II) fluoride.

[0027] In still another embodiment, the transition metal catalyst isgold(I) chloride.

[0028] In still other embodiments of the invention, the transition metalcatalyst is(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),N,N-bis(salicylidene)ethylenediaminocobalt(II) or(R,R)-(−)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II).

[0029] In another embodiment, X is methylene.

[0030] In other embodiments, R is hydrogen, hydroxyl, oxo or acetamido.

[0031] For example, R₁ to R₅ are each hydrogen; or R₁ is nitro, R₃ ischloro or trifluoromethyl, and R₂, R₄ and R₅ are hydrogen; or R₁ and R₃are bromo, and R₂, R₄ and R₅ are hydrogen.

[0032] In another embodiment, R₆ and R₇ are each methyl.

[0033] In another embodiment, R₁ and R₃ are each bromo or chloro.

[0034] A further aspect of this invention is the addition of pyridine tothe reaction mixture either as a component of the reaction mixture or asthe solvent in the presence of the transition metal catalyst. Pyridinehas been found to increase further the yield of the reaction as well ashaving superior solvent properties in certain cases. For example, whenthe diazonium salt is made using sodium nitrite and hydrochloric acid,pyridine also serves as a basic medium for neutralizing excess acid.

[0035] The stabilization of diazonium salts by pyridine has beenreported by Heinrich Zollinger et al. (Helv. Chimica Acta, 59, 1438(1976). Furthermore it is stated that pyridine promotes a homolyticradical pathway. Without a transition metal catalyst, however, thehomolytic cleavage at 70° C. is slow and is not useful.

[0036] The instant invention also pertains to a composition stabilizedwhich comprises

[0037] (a) an organic material subject to degradation by heat, light oroxygen, and

[0038] (b) an effective stabilizing amount of a compound of formula I,II or III as described above.

[0039] For example, the organic material is a natural, semi-synthetic orsynthetic polymer, especially a thermoplastic polymer.

[0040] In another embodiment, the polymer is a polyolefin orpolycarbonate; for example, polyethylene or polypropylene; or ispolypropylene; or the polymer is a styrenic, ABS, a nylon, a polyestersuch as poly(ethylene terephthalate) or poly(butylene terephthalate), apolyurethane, an acrylate, a rubber modified styrenic, poly(vinylchloride), poly(vinyl butyral), polyacetal (polyoxymethylene),poly(ethylene naphthalenedicarboxylate), or other blends or copolymerssuch as poly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETGor an ionomer as described on page 29.

[0041] In another embodiment of the instant invention, the organicmaterial is a resin selected from the group consisting of a thermosetacrylic melamine resin, an acrylic urethane resin, an epoxy carboxyresin, a silane modified acrylic melamine, an acrylic resin withcarbamate pendant groups crosslinked with melamine or an acrylic polyolresin crosslinked with melamine containing carbamate groups.

[0042] For example, the resin is a thermoset acrylic melamine resin oran acrylic urethane resin.

[0043] In yet another embodiment of the instant invention, the organicmaterial is a recording material.

[0044] The recording materials according to the invention are suitablefor pressure-sensitive copying systems, photocopying systems usingmicrocapsules, heat-sensitive copying systems, photographic materialsand ink jet printing.

[0045] The recording materials according to the invention aredistinguished by an unexpected improvement in quality, especially withregard to the fastness to light.

[0046] The recording materials according to the invention have theconstruction known for the particular use. They consist of a customarycarrier, for example, paper or plastic film, which has been coated withone or more layers. Depending on the type of material, these layerscontain the appropriate necessary components, in the case ofphotographic materials, for example, silver halide emulsions, dyecouplers, dyes and the like. Material particularly suitable for ink jetprinting has a layer particularly absorptive for ink on a customarycarrier. Uncoated paper can also be employed for ink jet printing. Inthis case the paper acts at the same time as the carrier material and asthe ink-absorbent layer. Suitable material for ink jet printing is, forexample, described in U.S. Pat. No. 5,073,448 which is incorporatedherein by reference.

[0047] The recording material can also be transparent as, for example,in the case of projection films.

[0048] The compounds of formula I, II or III can be incorporated intothe carder material as early as the production of the latter, in theproduction of paper, for example, being added to the paper pulp. Asecond method of application is to spray the carder material with anaqueous solution of compounds of formula I, II or III or to add thecompounds to the coating composition.

[0049] Coating compositions intended for transparent recording materialssuitable for projection cannot contain any particles which scatterlight, such as pigments and fillers.

[0050] The dye-binding coating composition can contain a number of otheradditives, for example, antioxidants, light stabilizers (including alsoUV absorbers which do not fall under the scope of the UV absorbers ofthis invention), viscosity improvers, fluorescent brighteners, biocidesand/or antistatic agents.

[0051] The coating composition is usually prepared as follows: thewater-soluble components, for example, the binder, are dissolved inwater and stirred together; the solid components, for example, fillersand other additives already described, are dispersed in this aqueousmedium; and disperison is advantageously carried out by means ofdevices, for example, ultrasonic systems, turbine stirrers,homogenizers, colloid mills, bead mills, sand mills, high-speed stirrersand the like. The compounds of formula I, II or III can be easilyincorporated into the coating composition.

[0052] The recording material according to this invention contains 1 to5000 mg/m²; or 50-1200 mg/m², of a compound of formula I, II or III.

[0053] As already mentioned, the recording materials according to theinvention embrace a wide field. The compounds of formula I, II or IIIcan, for example, be employed in pressure-sensitive copying systems.They can be introduced either into the paper in order to protect themicroencapsulated dye precursors there from light, or into the binder ofthe developer layer in order to protect the dyes formed there.

[0054] Photocopying systems using light-sensitive microcapsules whichare developed by means of pressure are described in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463; 4,551,407;4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A 162,664; EP-A164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129. In all thesesystems, the compounds can be put into the dye-receiving layer. Thecompounds can, however, also be put into the donor layer in order toprotect the color formers from light.

[0055] Photographic materials which can be stabilized are photographicdyes and layers containing such dyes or precursors thereof, for example,photographic paper and films. Suitable materials are, for example,described in U.S. Pat. No. 5,364,749 which is incorporated herein byreference. The compounds of formula I, II or III act here as a UV filteragainst electrostatic flashes. In color photographic materials, couplersand dyes are also protected against photochemical decomposition.

[0056] The instant compounds can be used for all types of colorphotographic materials. For example, they can be employed for colorpaper, color reversal paper, direct-positive color material, colornegative film, color positive film, color reversal film and the like.They are used inter alia for photographic color material which containsa reversal substrate or form positives.

[0057] Color-photographic recording materials usually contain, on asupport, a blue-sensitive and/or a green-sensitive and/or ared-sensitive silver halide emulsion layer and, if desired, a protectionlayer, with the instant compounds being, preferably, either in thegreen-sensitive or the red-sensitive layer or in a layer between thegreen-sensitive and the red-sensitive layer or in a layer on top of thesilver halide emulsion layers.

[0058] The compounds of formula I, II or III can also be employed inrecording materials based on the principles of photopolymerization,photoplasticization or the rupture of microcapsules, or in cases whereheat-sensitive and light-sensitive diazonium salts, leuko dyes having anoxidizing agent or dye lactones having Lewis acids are used.

[0059] Furthermore, the instant compounds can be employed in recordingmaterials for dye diffusion transfer printing, thermal wax transferprinting and non-matrix printing and for use with electrostatic,electrographic, electrophoretic, magnetographic andlaser-electrophotographic printers and pen-plotters. Of the above,recording materials for dye diffusion transfer printing are useful, forexample, as described in EP-A 507,734.

[0060] The instant compounds can also be employed in inks, preferablyfor ink jet printing, for example, as described in U.S. Pat. No.5,098,477 which is incorporated herein by reference.

[0061] The compounds of this invention exhibit superior hydrolyticstability, handling and storage stability as well as good resistance toextractability when present in a stabilized composition.

[0062] The methodology to make the instant compounds is described in theprior art. The intermediates needed to make the instant compounds arelargely items of commerce.

[0063] Some compounds are those in which one of X and Y is —O—; andthose in which both X and Y are —O—.

[0064] In general polymers which can be stabilized include

[0065] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),branched low density polyethylene (BLDPE).

[0066] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0067] a) radical polymerisation (normally under high pressure and atelevated temperature).

[0068] b) catalytic polymerisation using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerisation medium. The catalysts can be used by themselves inthe polymerisation or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, IIa and/or IIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0069] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0070] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0071] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

[0072] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0073] 6. Copolymers of styrene or α-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene,styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer, and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

[0074] 7. Graft copolymers of styrene or α-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

[0075] 8. Halogen-containing polymers such as polychloroprene,chlorinated rubbers, chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

[0076] 9. Polymers derived from α,β-unsaturated acids and derivativesthereof such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylonitriles, impact-modifiedwith butyl acrylate.

[0077] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

[0078] 11. Polymers derived from unsaturated alcohols and amines or theacyl derivatives or acetals thereof, for example polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

[0079] 12. Homopolymers and copolymers of cyclic ethers such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0080] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain ethylene oxide as a comonomer;polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0081] 14. Polyphenylene oxides and sulfides, and mixtures ofpolyphenylene oxides with styrene polymers or polyamides.

[0082] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0083] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, for example polyamide 4, polyamide 6, polyamide6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromaticpolyamides starting from m-xylene diamine and adipic acid; polyamidesprepared from hexamethylenediamine and isophthalic or/and terephthalicacid and with or without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

[0084] 17. Polyureas, polyimides, polyamide-imides andpolybenzimidazoles.

[0085] 18. Polyesters derived from dicarboxylic acids and diols and/orfrom hydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

[0086] 19. Polycarbonates and polyester carbonates.

[0087] 20. Polysulfones, polyether sulfones and polyether ketones.

[0088] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0089] 22. Drying and non-drying alkyd resins.

[0090] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0091] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

[0092] 25. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, polyisocyanates or epoxyresins.

[0093] 26. Crosslinked epoxy resins derived from polyepoxides, forexample from bisglycidyl ethers or from cycloaliphatic diepoxides.

[0094] 27. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, for examplecellulose acetates, cellulose propionates and cellulose butyrates, orthe cellulose ethers such as methyl cellulose; as well as rosins andtheir derivatives.

[0095] 28. Blends of the aforementioned polymers (polyblends), forexample PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.

[0096] 29. Naturally occurring and synthetic organic materials which arepure monomeric compounds or mixtures of such compounds, for examplemineral oils, animal and vegetable fats, oil and waxes, or oils, fatsand waxes based on synthetic esters (e.g. phthalates, adipates,phosphates or trimellitates) and also mixtures of synthetic esters withmineral oils in any weight ratios, typically those used as spinningcompositions, as well as aqueous emulsions of such materials.

[0097] 30. Aqueous emulsions of natural or synthetic rubber, e.g.natural latex or latices of carboxylated styrene/butadiene copolymers.

[0098] 31. Polysiloxanes such as the soft, hydrophilic polysiloxanesdescribed, for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

[0099] 32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

[0100] 33. Radiation curable compositions containing ethylenicallyunsaturated monomers or oligomers and a polyunsaturated aliphaticoligomer.

[0101] 34. Epoxymelamine resins such as light-stable epoxy resinscrosslinked by an epoxy functional coetherified high solids melamineresin such as LSE-4103 (Monsanto).

[0102] In general, the compounds of the present invention are employedin from about 0.01 to about 5% by weight of the stabilized composition,although this will vary with the particular substrate and application.An advantageous range is from about 0.05 to about 3%, and especially0.05 to about 1%. However, some high performance films or in UVabsorbing layers of laminates such as those produced by coextrusion maycontain from 5-15% by weight of the instant compounds. Concentrations of5-10% by weight are typical in certain coextrusion applications.

[0103] The stabilizers of the instant invention may readily beincorporated into the organic polymers by conventional techniques, atany convenient stage prior to the manufacture of shaped articlestherefrom. For example, the stabilizer may be mixed with the polymer indry powder form, or a suspension or emulsion of the stabilizer may bemixed with a solution, suspension, or emulsion of the polymer. Theresulting stabilized polymer compositions of the invention mayoptionally also contain from about 0.01 to about 5%, preferably fromabout 0.025 to about 2%, and especially from about 0.1 to about 1% byweight of various conventional additives, such as the materials listedbelow, or mixtures thereof.

[0104] 1. Antioxidants

[0105] 1.1. Alkylated monophenols, for example,

[0106] 2,6-di-tert-butyl-4-methylphenol

[0107] 2-tert-butyl-4,6-dimethylphenol

[0108] 2,6-di-tert-butyl-4-ethylphenol

[0109] 2,6-di-tert-butyl-4-n-butylphenol

[0110] 2,6-di-tert-butyl-4-i-butylphenol

[0111] 2,6-di-cyclopentyl-4-methylphenol

[0112] 2-(α-methylcyclohexyl)-4,6-dimethylphenol

[0113] 2,6-di-octadecyl-4-methylphenol

[0114] 2,4,6-tri-cyclohexylphenol

[0115] 2,6-di-tert-butyl-4-methoxymethylphenol

[0116] 1.2. Alkylated hydroquinones, for example,

[0117] 2,6-di-tert-butyl-4-methoxyphenol

[0118] 2,5-di-tert-butyl-hydroquinone

[0119] 2,5-di-tert-amyl-hydroquinone

[0120] 2,6-diphenyl-4-octadecyloxyphenol

[0121] 1.3. Hydroxylated thiodiphenyl ethers, for example,

[0122] 2,2′-thio-bis-(6-tert-butyl-4-methylphenol)

[0123] 2,2′-thio-bis-(4-octylphenol)

[0124] 4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

[0125] 4,4′-thio-bis-(6-tert-butyl-2-methylphenol)

[0126] 1.4. Alkylidene-bisphenols, for example,

[0127] 2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)

[0128] 2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

[0129] 2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

[0130] 2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)

[0131] 2,2′-methylene-bis-(6-nonyl-4-methylphenol)

[0132] 2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

[0133] 2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

[0134] 2,2′-methylene-bis-(4,6-di-tert-butylphenol)

[0135] 2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

[0136] 2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

[0137] 4,4′-methylene-bis-(2,6-di-tert-butylphenol)

[0138] 4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

[0139] 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0140] 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

[0141] 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0142]1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

[0143] ethyleneglycolbis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

[0144] di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

[0145]di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

[0146] 1.5. Benzyl compounds, for example,

[0147]1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

[0148] di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

[0149] 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctylester

[0150] bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate

[0151] 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

[0152] 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

[0153] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecylester

[0154] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethylester, calcium-salt

[0155] 1.6. Acylaminophenols, for example,

[0156] 4-hydroxy-lauric acid anilide

[0157] 4-hydroxy-stearic acid anilide

[0158]2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

[0159] octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

[0160] 1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid with monohydric or polyhydric alcohols, for example,

[0161] methanol

[0162] diethylene glycol

[0163] octadecanol

[0164] triethylene glycol

[0165] 1,6-hexanediol

[0166] pentaerythritol

[0167] neopentyl glycol

[0168] tris-hydroxyethyl isocyanurate

[0169] thiodiethylene glycol

[0170] di-hydroxyethyl oxalic acid diamide

[0171] triethanolamine

[0172] triisopropanolamine

[0173] 1.8. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydricor polyhydric alcohols, for example,

[0174] methanol

[0175] diethylene glycol

[0176] octadecanol

[0177] triethylene glycol

[0178] 1,6-hexanediol

[0179] pentaerythritol

[0180] neopentyl glycol

[0181] tris-hydroxyethyl isocyanurate

[0182] thiodiethylene glycol

[0183] di-hydroxyethyl oxalic acid diamide

[0184] triethanolamine

[0185] triisopropanolamine

[0186] 1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid for example,

[0187]N,N′-d-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

[0188]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

[0189] N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

[0190] 1.10 Diarylamines, for example,

[0191] diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,

[0192] 4,4′-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and

[0193] 2,4,4-trimethylpentene, reaction product of diphenylamine and2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and2,4,4-trimethylpentene.

[0194] 2. UV absorbers and light stabilizers

[0195] 2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the5′-methyl-, 3′,5′-di-tert-butyl-, 5′-tert-butyl-,5′-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3′,5′-di-tert-butyl-,5-chloro-3′-tert-butyl-5′-methyl-, 3′-sec-butyl-5′-tert-butyl-,4′-octoxy, 3′,5′-di-tert-amyl-, 3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3′-dodecyl-5′-methyl-, and 3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-,and dodecylated-5′-methyl derivatives.

[0196] 2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-,4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy,4,2′,4′-trihydroxy- and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0197] 2.3. Esters of optionally substituted benzoic acids for example,phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

[0198] 2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acidethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methylester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butylester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

[0199] 2.5. Nickel compounds, for example, nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

[0200] 2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

[0201] 2.7. Oxalic acid diamides, for example,4,4′-di-octyloxy-oxanilide,2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

[0202] 2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

[0203] 3. Metal deactivators, for example, N,N′-diphenyloxalic aciddiamide, N-salicylal-N′-salicyloylhydrazine,N,N′-bis-salicyloylhydrazine,N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

[0204] 4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4′-diphenylylenediphosphonite.

[0205] 5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

[0206] 6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0207] 7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

[0208] 8. Amine Oxides, for example, tridecyl amine oxide, tridodecylamine oxide, trihexadecyl amine oxide, tri(C₁₂-C₁₄ alkyl) amine oxide,tri(C₁₆-C₁₈ alkyl) amine oxide, tri(C₂₀-C₂₂ alkyl) amine oxide,di(C₁₂-C₁₄ alkyl) methyl amine oxide, di(C₁₆-C₁₈ alkyl) methyl amineoxide, di(C₂₀-C₂₂ alkyl) methyl amine oxide, di(tallow alkyl) methylamine oxide, di(coco alkyl) methyl amine oxide.

[0209] 9. Polyamide stabilizers, for example copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

[0210] 10. Basic co-stabilizers, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acidsfor example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and Kpalmitate, antimony pyrocatecholate or zinc pyrocatecholate.

[0211] 11. Nucleating agents, for example, 4-tert-butyl-benzoic acid,adipic acid, diphenylacetic acid.

[0212] 12. Fillers and reinforcing agents, for example, calciumcarbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, bariumsulfate, metal oxides and hydroxides, carbon black, graphite.

[0213] 13. Other additives, for example, plasticizers, lubricants,emulsifiers, pigments, optical brighteners, flameproofing agents,anti-static agents, blowing agents and thiosynergists such as dilaurylthiodipropionate or distearyl thiodipropionate.

[0214] 14. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No.5,175,312, or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0215] The co-stabilizers, with the exception of the benzofuranoneslisted under 14, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

[0216] Further compositions comprise, in addition to components (a) and(b) further additives, such as phenolic antioxidants, light stabilizersor processing stabilizers.

[0217] These additives are phenolic antioxidants (item 1 of the list),sterically hindered amines (item 2.6 of the list), phosphites andphosphonites (item 4 of the list), UV absorbers (item 2 of the list) andperoxide-destroying compounds (item 5 of the list).

[0218] Additional additives (stabilizers) which are also thebenzofuran-2-ones, such as described, for example, in U.S. Pat. No.4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

[0219] For examples, the phenolic antioxidant is selected from the groupconsisting of

[0220] n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,neopentanetetrayl

[0221] tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate),di-n-octadecyl

[0222] 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,

[0223] 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylene

[0224] bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,

[0225] 2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate,

[0226] 1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene

[0227] bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate],

[0228] octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,

[0229] bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and

[0230]N,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

[0231] Another embodiment is the phenolic antioxidant which isneopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

[0232] The hindered amine compound is selected from the group consistingof

[0233] bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

[0234] bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,

[0235] di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,

[0236] 4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,

[0237]3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,

[0238] tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,

[0239] 1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane,

[0240] tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,

[0241] tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,

[0242] polycondensation product of 2,4-dichloro-6-morpholino-s-triazineand 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate,

[0243] mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethylpiperidin-4-carboxylate),

[0244] 4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,

[0245] di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,

[0246]poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],and

[0247]2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

[0248] Another hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

[0249] The instant composition can additionally contain another UVabsorber selected from the group consisting of the benzotriazoles,s-triazines, the oxanilides, the hydroxybenzophenones, benzoates and theα-cyanoacrylates.

[0250] The instant composition may additionally contain an effectivestabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

[0251] The 2-hydroxyphenyl-2H-benzotriazole is selected from the groupconsisting of

[0252] 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

[0253] 2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

[0254]2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

[0255]2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;

[0256] 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0257]5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

[0258] 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; and

[0259]2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

[0260] The other tris-aryl-s-triazine is selected from the groupconsisting of

[0261]2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

[0262] 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;

[0263]2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine;and

[0264]2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-triazine.

[0265] The alkyd resin lacquers which can be stabilized against theaction of light and moisture in accordance with the instant inventionare the conventional stoving lacquers which are used in particular forcoating automobiles (automobile finishing lacquers), for examplelacquers based on alkyd/melamine resins and alkyd/acrylic/melamineresins (see H. Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages99-123). Other crosslinking agents include glycouril resins, blockedisocyanates or epoxy resins.

[0266] The lacquers stabilized in accordance with the invention aresuitable both for metal finish coatings and solid shade finishes, suchas in the case of retouching finishes, as well as various coil coatingapplications. The lacquers stabilized in accordance with the inventionare applied in the conventional manner by two methods, either by thesingle-coat method or by the two-coat method. In the latter method, thepigment-containing base coat is applied first and then a covering coatof clear lacquer over it.

[0267] It is also to be noted that the compounds of the presentinvention are applicable for use in non-acid catalyzed thermoset resinssuch as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyesterresins, optionally modified with silicon, isocyanates or isocyanurates.The epoxy and epoxy-polyester resins are crosslinked with conventionalcrosslinkers such as acids, acid anhydrides, amines and the like.Correspondingly, the epoxide may be utilized as the crosslinking agentfor various acrylic or polyester resin systems that have been modifiedby the presence of reactive groups on the backbone structure.

[0268] When used in two-coat finishes, the compounds of the instantinvention can be incorporated in the clear coat or both in the clearcoat and in the pigmented base coat.

[0269] When water-soluble, water miscible or water dispersible coatingare desired ammonium salts of acid groups present in the resin areformed. Powder coating composition can be prepared by reacting glycidylmethacrylate with selected alcohol components.

[0270] The instant benzotriazoles are made by conventional methods forpreparing such compounds. The usual procedure involves the diazotizationof a substituted o-nitroaniline followed by coupling the resultantdiazonium salt with a substituted phenol and reduction of the azobenzeneintermediate to the corresponding desired benzotriazole. The startingmaterials for these benzotriazoles are largely items of commerce or canbe prepared by normal methods of organic synthesis.

[0271] While the instant benzotriazoles with their enhanced durabilityare particularly suited for automotive coating applications, it iscontemplated that they will also be especially useful in otherapplications where their enhanced durability is required such as insolar films and the like.

[0272] Some of the instant compounds of formulas I, II, III, IV, V or VIare novel. These include

[0273] (i)1-(2-nitro-4-trifluoromethylphenoxy)-2,2,6,6-tetramethylpiperidine;

[0274] (ii) 1-(2-nitro-4-chlorophenoxy)-2,2,6,6-tetramethylpiperidine;

[0275] (iii) 1-(2,4-dibromophenoxy)-2,2,6,6-tetramethylpiperidine;

[0276] (iv)1-(2,4-dibromophenoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine;

[0277] (v)1-(2,4-dibromophenoxy)-4-acetamido-2,2,6,6-tetramethylpiperidine;

[0278] (vi) 1-(2,4-dibromophenoxy)-4-oxo-2,2,6,6-tetramethylpiperidine;

[0279] (vii) 1-(2-naphthyloxy)-2,2,6,6-tetramethylpiperidine;

[0280] (viii) 1-(4-benzoylphenoxy)-2,2,6,6-tetramethylpiperidine;

[0281] (ix) 1-phenoxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine;

[0282] (x) N-phenoxy-di-tert-butylamine;

[0283] (xi)2,4-bis[N-butyl-N-(1-phenoxy-2,2,6,6-tetra-methylpiperidin-4-yl)amino]-6-chloro-s-triazine;

[0284] (xii)2,4-bis{N-butyl-N-[1-(2,4-dibromophenoxy)-2,2,6,6-tetramethylpiperidin-4-yl]amino}-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine;

[0285] (xiii)2,4-bis[N-butyl-N-(1-phenoxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine;

[0286] (xiv) 1-(3,5-di-tert-butylphenoxy)-2,2,6,6-tetramethylpiperidine;

[0287] (xv) 1-(pyridin-3-yloxy)-2,2,6,6-tetramethylpiperidine;

[0288] (xvi)1-(2-nitro-4-chlorophenoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidine;

[0289] (xvii)4,4′-bis(2,2,6,6-tetramethylpiperidin-1-yloxy)benzophenone;

[0290] (xviii) di(1-phenoxy-2,2,6,6-tetramethyl-piperidin-4-yl)sebacate;

[0291] (xix)5-[4-(2,2,6,6-tetramethylpiperidin-1-yloxy)-phenyl]-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0292] (xx)4,4′-bis[(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxy]diphenylmethane,or

[0293] (xxi)1-(phthalimid-4-yloxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine.

[0294] Still another embodiment of the instant invention is acomposition which comprises

[0295] (a) candle wax which is white and scented, white and unscented,dyed and scented, dyed and unscented, dipped and scented or dipped andunscented, and

[0296] (b) an effective stabilizing amount of a compound of formula I,II or III as described above.

[0297] It should be noted that candles contain a host of variouscomponents. The base materials may be made up of the following:

[0298] paraffin wax,

[0299] natural oils,

[0300] polyamide plus fatty acid/ester,

[0301] fatty acids such as stearin,

[0302] opacifiers,

[0303] beeswax,

[0304] glycerides plus oxidized wax,

[0305] alcohols, and

[0306] ethylene oligomers.

[0307] Candles also contain a number of additives such as the following:

[0308] mold release agents,

[0309] fragrances,

[0310] insect repellants or insecticides,

[0311] hardeners,

[0312] crystal modifiers,

[0313] clarifiers,

[0314] guttering reducers,

[0315] colorants,

[0316] f.p. control agents,

[0317] stretchability improvers,

[0318] gelling agents,

[0319] extrusion aids, and

[0320] vortex reducers.

[0321] Each of the various components are meant to control or modify theproperties of the candle to insure proper burning, reduce channelling,aid in uniform melting, and the like. The colorants and fragrancesobviously are there to provide the proper color, scent or otheraesthetic appeal.

[0322] Of increasing importance are the transparent gel candles whichlook like clear glass, but which bum like a classical candle. As isdiscussed in detail in U.S. Pat. No. 5,879,694, the relevant parts ofwhich are incorporated herein by reference, these gel candles usuallycontain a copolymer selected from the group consisting of a triblock,radial block, diblock or multiblock copolymer classically made up of atleast two thermodynamically incompatible segments containing both hardand soft segments. Typical of such block copolymers is KRATON® (ShellChemical Co.) which consists of block segments of styrene monomer unitsand rubber monomer or comonomer units. The most common structure foundin KRATON® series is a linear ABA block with styrene-butadiene-styrene(SBS) or styrene-isoprene-styrene (SIS).

[0323] The following examples are for illustrative purposes only and arenot to be construed to limit the scope of the invention in any mannerwhatsoever.

EXAMPLE 1 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0324] This example shows the use of 0.3 mol % of copper(II) fluoridebased on aniline and with 3 molar excess of aniline.

[0325] To a suspension of 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 11.76 g (114 mmol) of tert-butylnitrite and 25 mg (0.25 mmol) of copper(II) fluoride in 120 mL ofacetonitrile at 65° C. under a nitrogen atmosphere is added dropwiseover 30 minutes 6.98 g (75 mmol) of aniline. The evolution of gas isobserved during the addition of the aniline. The dark red reactionmixture is kept at 65° C. for an additional ten minutes followed bycooling to ambient temperature. The reaction mixture is thenconcentrated to a thick oil which turns into a semi-solid upon standing.The residue is purified by vacuum flash chromatography (heptane) to give4.3 g of a colorless oil in 74.1% yield based on nitroxyl. The structureis confirmed by ¹Hnmr analysis, mass spectroscopy and elementalanalyses.

[0326]¹Hnmr (C₆D₆) (300.08 MHz) d 1.42, 1.20, 1.12 (overlapping m, CH₂,6H), 1.16 (s, CH₃, 6H), 1.017 (s, CH₃, 6H), 7.25 (d, 2H, ³J_(HH′)=8.2Hz), 7.12 (dd, CH, 2H. ³J_(HH′)=8.3 Hz), ³J_(HH″)=8.2 Hz), 6.78 (tt, CH,1H, ³J_(HH′)=7.2 Hz, ⁴J_(HH″)=1.2 Hz); MS m/s 233.

[0327] Analysis: Calcd for C₁₅H₂₃NO: C, 77.2; H, 9.9; N, 6.0. Found: C,77.1; H, 9.9; N, 6.0.

EXAMPLE 2 1-Phenoxy-2,2,6,6-tetramethyl-4-hydroxypiperidine

[0328] The procedure of Example 1 is repeated using 17.2 g (100 mmol) of1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 3.92 g (38 mmol) oftert-butyl nitrite, 3 g (30 mmol) of copper(II) fluoride, 120 mL ofacetonitrile and 2.32 g (25 mmol) of aniline at 65° C. The crude productobtained is purified by vacuum flash chromatography (25% ethylacetate/heptane) to give 3.3 g of a solid melting at 144-146° C., a 53%yield based on the aniline. The structure is confirmed by ¹Hnmr and massspectroscopy analyses.

[0329]¹Hnmr (CDCl₃) (300.08 MHz) d 1.94, 1.76, 1.62 (overlapping m, CH₂,4H), 1.30 (s, CH₃, 6H), 1.07 (s, CH₃, 6H), 4.05 (m, CH, 1H), 7.22(overlapping m, CH, 4H), 6.87 (tt, CH, 1H, ³J_(HH′)=6.8 Hz, ⁴J_(HH″)=1.6Hz); MS m/s 249.

[0330] Analysis: Calcd for C₁₅H₂₃NO₂: C, 72.3; H, 9.3; N, 5.6. Found: C,72.2; H, 9.3; N, 5.4.

EXAMPLE 3 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0331] This example shows the effect of excess nitroxyl and a greaterthan stoichiometric amount of copper(II) fluoride catalyst.

[0332] Into a suspension of 15.6 g (100 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 3.92 g (38 mmol) of tert-butylnitrite and 3 g (30 mmol) of copper(II) fluoride in 120 mL ofacetonitrile at 65° C. is added dropwise 2.32 g (25 mmol) of aniline.During the addition, the evolution of gas is observed. After 30 minutesof addition time, the dark red reaction mixture is kept at 65° C. for anadditional ten minutes followed by cooling to ambient temperature. Thereaction mixture is then concentrated to a thick oil which turns into asemi crude solid on standing. The crude product is purified by vacuumflash chromatography (heptane) to give 2.3 g of a colorless oil in 39.6%yield based on the starting aniline. The structure of the product isconfirmed by ¹Hnmr and mass spectroscopy analyses.

[0333]¹Hnmr (C₆D₆) (300.08 MHz) d 1.42, 1.29, 1.12 (overlapping m, CH₂,6H), 1.16 (s, CH₃, 6H), 1.017 (s, CH₃, 6H), 7.25 (d, 2H, ³J_(HH′)=8.2Hz), 7.12 (dd, CH, 2H, ³J_(HH′)=8.3 Hz), ³J_(HH″)=8.2 Hz), 6.78 (tt, CH,1H, ³J_(HH′)=7.2 Hz, ⁴J_(HH″)=1.2 Hz); MS m/s 233.

EXAMPLE 4 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0334] This example shows the effect of excess nitroxyl and 5.2 mol %copper(II) catalyst

[0335] The procedure of Example 1 is repeated using 15.6 g (100 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 3.92 g (38 mmol) of tert-butylnitrite, 0.13 g (1.3 mmol (of copper(II) fluoride, 120 mL ofacetonitrile and 2.32 g (25 mmol) of aniline at 65° C. The crude productis purified by vacuum flash chromatography (heptane) to give 2.8 g ofcolorless oil in a 48% yield based on the aniline.

EXAMPLE 5 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0336] This example shows the effect of temperature on the reaction.Example 4 is repeated at room temperature.

[0337] The procedure of Example 1 is repeated using 15.6 g (100 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 3.92 g (38 mmol) of tert-butylnitrite, 0.13 g (1.3 mmol) of copper(II) fluoride, 120 mL ofacetonitrile and 2.32 g (25 mmol) of aniline at ambient temperature for72 hours. The crude product is purified by vacuum flash chromatography(heptane) to give 3.0 g of colorless oil in a 52% yield based on theaniline.

EXAMPLE 6 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0338] This experiment shows the effect of having a 2 molar excess ofaniline and 0.5 mol % of copper(II) fluoride catalyst.

[0339] The procedure of Example 1 is repeated using 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 7.84 g (76 mmol) of tert-butylnitrite, 25 mg (0.25 mmol) of copper(II) fluoride, 120 mL ofacetonitrile and 4.65 g (50 mmol) of aniline at 65° C. The crude productis purified by vacuum flash chromatography (heptane) to give 3.8 g ofcolorless oil in a 66% yield based on nitroxyl.

EXAMPLE 7 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0340] This example shows the effect of temperature on the instantprocess. Example 6 is repeated at room temperature.

[0341] The procedure of Example 1 is repeated using 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 7.84 g (76 mmol) of tert-butylnitrite, 25 mg (0.25 mmol) of copper(II) fluoride, 120 mL ofacetonitrile and 4.65 g (50 mmol) of aniline at ambient temperature for72 hours. The crude product is purified by vacuum flash chromatography(heptane) to give 2.5 g of colorless oil in a 43% yield based onnitroxyl.

EXAMPLE 8 1-Phenoxy-2,2,6,6-tetramethyl-4-hydroxypiperidine

[0342] This example shows the effect of excess nitroxyl and 5 mol %copper(II) fluoride catalyst.

[0343] The procedure of Example 1 is repeated using 17.2 g (100 mmol) of1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 3.92 g (38 mmol) oftert-butyl nitrite, 0.13 g (1.3 mmol) of copper(II) fluoride, 120 mL ofacetonitrile and 2.32 g (25 mmol) of aniline at 65° C. The crude productis purified by vacuum flash chromatography (25 ethyl acetate/heptane) togive 3.4 g of colorless oil in a 55% yield based on the aniline.

EXAMPLE 91-(2-Nitro-4-trifluoromethylphenoxy)-2,2,6,6-tetramethylpiperidine

[0344] The procedure of Example 1 is repeated using 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 7.84 g (76 mmol) oftert-butyl nitrite, 25 mg (0.25 mmol) of copper(II) fluoride, 120 mL ofacetonitrile and 10.3 g (50 mmol) of 2-nitro-4-trifluoromethylaniline at65° C. The crude product obtained is purified by vacuum flashchromatography (heptane) to give 6.0 g of light yellow crystals meltingat 54-55° C., a 68.9% yield based on nitroxyl. The structure isconfirmed by ¹Hnmr, mass spectroscopy and elemental analyses.

[0345]¹Hnmr (CDCl₃) (300.08 MHz) d 1.94, 1.76, 1.62 (overlapping m, CH₂,4H), 1.30 (s, CH₃, 6H), 1.07 (s, CH₃, 6H), 4.05 (m, CH, 1H), 7.22(overlapping m, CH, 4H), 6.87 (tt, CH, 1H, ³J_(HH′)=6.8 Hz, ⁴J_(HH″)=1.6Hz); MS m/s 249.

[0346] Analysis: Calcd for C₁₆H₂₁F₃N₂O₃: C, 55.4; H, 6.1; N, 8.1. Found:C, 55.4; H, 6.2; N, 8.1.

EXAMPLE 101-(2,4-Dibromophenoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine

[0347] The procedure of Example 1 is repeated using 12.8 g (74 mmol) of1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 14.23 g (138 mmol) oftert-butyl nitrite, 0.73 g (0.74 mmol) of copper(II) fluoride, 200 mL ofpyridine and 8.56 g (92 mmol) of 2,4-dibromoaniline at 65° C. The crudeproduct obtained is purified by vacuum flash chromatography (5% ethylacetate/heptane) to give 17 g of the title compound as a yellowish solidsolid in 63.5% yield. The structure is confirmed by ¹Hnmr analysis.

[0348]¹Hnmr (C₆D₆) (300.08 MHz) d 1.62 1.95 (overlapping m, CH₂, 4H),1.01 (s, CH₃, 6H), 1.34 (s, CH₃, 6H), 4.09 (m, OCH, 1H), 7.29 (dd, CH,1H, ³J_(HH′)=8.9 Hz, ⁴J_(HH″)=2.3 Hz), 7.43 (d, CH, 1H, ³J_(HH′)=9.4Hz), 7.58 (d, CH, 1H, ⁴J_(HH′)=2.3 Hz).

EXAMPLE 11 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0349] This example shows the use of a mixture of acetonitrile andpyridine as the reaction medium.

[0350] The process of Example 1 is repeated using 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 7.84 g (76 mmol) of tert-butylnitrite, 25 mg (0.25 mmol) of copper(II) fluoride in a mixture of 100 mLof acetonitrile/20 mL of pyridine and 4.65 g (50 mmol) of aniline in 10mL of acetonitrile at 70° C. The crude product obtained is purified byvacuum flash chromatography (heptane) to give 4.9 g of the titlecompound as a colorless oil in 84.5% yield.

EXAMPLE 12 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0351] This example shows the use of pyridine alone as the reactionmedium.

[0352] The procedure of Example 1 is again repeated using 3.9 g (25mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidine, 7.84 g (76 mmol) oftert-butyl nitrite, 25 mg (0.25 mmol) of copper(II) fluoride in amixture of 120 mL of pyridine and 4.65 g (50 mmol) of aniline at 70° C.The crude product obtained is purified by vacuum flash chromatography(heptane) to give 4.8 g of the title compound as a colorless oil in82.8% yield.

EXAMPLE 13 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0353] This example shows the use of equal molar equivalents of nitroxylradical and aniline.

[0354] The procedure of Example 1 is repeated using 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 7.84 g (76 mmol) of tert-butylnitrite, 25 mg (0.25 mmol) of copper(II) fluoride in a mixture of 120 mLof pyridine and 2.32 g (25 mmol) of aniline at 70° C. The crude productformed is purified by vacuum flash chromatography (heptane) to give 4.5g of the title compound as a colorless oil in 77.6% yield.

EXAMPLE 14 1-(2-Nitro-4-chlorophenoxy)-2,2,6,6-tetramethylpiperidine

[0355] The procedure of Example 1 is repeated using 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 7.84 g (76 mmol) of tert-butylnitrite, 25 mg (0.25 mmol) of copper(II) fluoride, 120 mL of pyridineand 8.6 g (50 mmol) of 2-nitro-4-chloroaniline at 70° C. The crudeproduct obtained is purified by vacuum flash chromatography (heptane) togive 5.2 g of the title compound as a light yellow oil in 66.7% yield.The structure is confirmed by ¹Hnmr and mass spectroscopy analyses.

[0356]¹Hnmr (C₆D₆) (499.84 MHz) d 1.35, 1.28, 0.95 (overlapping m, CH₂,6H), 0.84 (s, CH₃, 6H), 1.14 (s, CH₃, 6H), 6.95 (dd, CH, 1H,³J_(HH′)=8.9 Hz, ⁴J_(HH″)=1.9 Hz), 7.44 (d, CH, ³J_(HH′)=8.9 Hz), 7.51(d, CH, 1H, ⁴J_(HH′)=1.9 Hz); MS m/z 312.

[0357] Analysis: Calcd for C₁₅H₂₁ClN₂O₃: C, 57.6; H, 6.7; N, 8.9. Found:C, 57.3; H, 6.5; N, 8.9.

EXAMPLE 15 1-(2,4-Dibromophenoxy)-2,2,6,6-tetramethylpiperidine

[0358] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 3.92 g (38 mmol) of tert-butylnitrite, 12.5 mg (0.125 mmol) of copper(II) fluoride, 120 mL of pyridineand 6.30 g (25 mmol) of 2,4-dibromoaniline at 70° C. The crude productobtained is purified by vacuum flash chromatography (heptane) to give3.34 g of the title compound as a light yellow oil in 68.5% yield. Thestructure is confirmed by ¹Hnmr analysis.

[0359]¹Hnmr (C₆D₆) (499.84 MHz) d 1.38, 1.25, 1.11 (overlapping m, CH₂,6H), 0.86 (s, CH₃, 6H), 1.22 (s, CH₃, 6H), 7.07 (dd, CH, 1H,³J_(HH′)=8.9 Hz, ⁴J_(HH″)=1.9 Hz), 7.23 (d, CH, 1H, ³J_(HH′)=8.9 Hz),7.52 (d, CH, 1H, ⁴J_(HH′)=1.9 Hz).

EXAMPLE 16 1-(4-Benzoylphenoxy)-2,2,6,6-tetramethylpiperidine

[0360] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 3.92 g (38 mmol) of tert-butylnitrite, 12.5 mg (0.125 mmol) of copper(II) fluoride, 120 mL of pyridineand 4.93 g (25 mmol) of 4-aminobenzophenone in 40 mL of pyridine at 70°C. The crude product obtained is purified by vacuum flash chromatography(heptane) to give 3.40 g of the title compound as a light yellow oil in80.6% yield. The structure is confirmed by ¹Hnmr, elemental and massspectrographic analysis.

[0361]¹Hnmr (CDCl₃) (300.08 MHz) d 1.63, 1.44 (overlapping m, CH₂, 6H),1.03 (s, CH₃, 6H), 1.26 (s, CH₃, 6H), 7.48, 7.55 (overlapping m, CH,4H), 7.78 (d, 1H, ³J_(HH′)=6.8 Hz, ⁴J_(HH″)=1.6 Hz); MS m/z 249.

[0362] Analysis: Calcd for C₂₂H₂₇NO₂: C, 78.3; H, 8.1; N, 4.2. Found: C,78.1; H, 8.0; N, 4.2.

EXAMPLE 17 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0363] This example shows the use of an aqueous diazotization withsodium nitrite and hydrochloric acid in place of tert-butyl nitrite inorganic medium.

[0364] Into a solution of 5 g of water and 15.3 g (150 mmol) ofconcentrated hydrochloric acid is added dropwise 4.60 g (50 mmol) ofaniline. The temperature of the reaction mixture during the additionstep is kept under 40° C. After the addition is complete, the reactionmixture is heated to 70° C. for one hour. The reaction mixture is thencooled to 0° to 5° C. followed by a dropwise addition of an aqueoussolution of 3.45 g (50 mmol) of sodium nitrite in 10 mL of water. Theaddition time is 20 minutes while the reaction temperature is maintainedat 0° to 5° C. The reaction mixture is transferred to a cold-jacketedaddition funnel and is then added dropwise into a solution of 3.9 g (25mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidine, 25 mg (0.25 mmol) ofcopper(II) fluoride in 120 mL of pyridine at 70° C. Evolution ofnitrogen is observed during the addition. After the addition iscomplete, the reaction mixture is kept at 70° C. for another 30 minutesfollowed by cooling to ambient temperature. The reaction mixture isconcentrated to a thick oil. The crude product is purified by vacuumflash chromatography (heptane) to give 3.97 g of the title as acolorless oil in 68.4% yield.

EXAMPLE 18 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0365] This example shows the use of various other transition metalcatalysts for preparing the title compound.

[0366] When the procedure of Example 1 is repeated by replacingcopper(II) fluoride with an equivalent amount of the followingcatalysts:

[0367] copper(I) chloride (72.4% yield);

[0368] cobalt(II) acetate (67% yield);

[0369] manganese(II) chloride;

[0370] ferrous chloride;

[0371] ferric chloride;

[0372] titanium (III) chloride;

[0373] the title compound is prepared in good yield.

EXAMPLE 19 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0374] This example shows the use of a two molar excess of aniline andpyridine, but first without copper(II) catalyst. No reaction occurs tillthe copper catalyst is added.

[0375] Into a solution of 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine and 3.92 g (39 mmol) of tert-butylnitrite in 120 mL of pyridine at 65-70° C. is added a solution of 2.32 g(25 mmol) of aniline. During the addition, no evolution of nitrogen isobserved. After 1.5 hours no product is observed by thin layerchromatography. Into the reaction mixture at 65-70° C., 25 mg (0.25mmol) of copper(II) fluoride is now added and a vigorous eveolution ofnitrogen is observed. After 15 minutes, the reaction mixture isconcentrated and purified by vacuum flash chromatography (heptane) togive 2.4 g of the title compound as a colorless oil in 41.4% yield.

EXAMPLE 20 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0376] This example shows the substitution of pyridine by diethylamineas solvent with two molar excess of aniline and 0.5 mole % copper(II)catalyst.

[0377] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 3.90 g (38 mmol) of tert-butylnitrite, 12.5 mg (0.125 mmol) of copper(II) fluoride, 120 mL oftriethylamine and 2.30 g (25 mmol) of aniline at 70° C. The crudeproduct is purified by vacuum flash chromatography (heptane) to give 2.3g of the title compound as a colorless oil in a 65.6% yield.

EXAMPLE 21 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0378] This example shows the use of a three molar excess of aniline and0.03 mole % cobalt(II) catalyst and pyridine.

[0379] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 4.12 g (40 mmol) of tert-butylnitrite, 7.5 mg (0.0125 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II)in a mixture of 120 mL of pyridine and 3.48 g (37.5 mmol) of aniline at70° C. The crude product is purified by vacuum flash chromatography(heptane) to give 2.67 g of the title compound as a colorless oil in a91.8% yield.

EXAMPLE 22 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0380] This example shows the use of a three molar excess of aniline and0.03 mole % cobalt(II) catalyst and pyridine.

[0381] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 4.12 g (40 mmol) of tert-butylnitrite, 4.01 mg (0.0125 mmol) ofN,N-bis(salicylidene)ethylenediaminocobalt(II) in a mixture of 120 mL ofpyridine and 3.48 g (37.5 mmol) of aniline at 70° C. The crude productis purified by vacuum flash chromatography (heptane) to give 2.64 g ofthe title compound as a colorless oil in a 90.7% yield.

EXAMPLE 23 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0382] This example shows the use of a two molar excess of aniline and0.03 mole % cobalt(II) catalyst and chlorobenzene.

[0383] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 3.09 g (30 mmol) of tert-butylnitrite, 7.5 mg (0.0125 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II)ina mixture of 120 mL of chlorobenzene and 2.33 g (25 mmol) of aniline at70° C. The crude product is purified by vacuum flash chromatography(heptane) to give 2.20 g of the title compound as a colorless oil in a75.6% yield.

EXAMPLE 24 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0384] The procedure of Example 21 is repeated, but substituting for the(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II)any one of the following catalysts:

[0385] cobalt(II) phthalocyanine;

[0386] 5,10,15,20-tetraphenyl-21H,23H-porphine cobalt(II);

[0387] 5,10,15,20-tetrakis(4-methoxyphenyl)-21H,23H-porphine cobalt(II);or

[0388] 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine cobalt(II).

EXAMPLE 25 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0389] This example shows the use of a two molar excess of aniline, 0.5mole % of copper(II) chloride and acetonitrile.

[0390] The procedure of Example 1 is repeated using 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, and 7.84 g (76 mmol) of tert-butylnitrite, 24 mg (0.25 mmol) of copper(II) chloride, 120 mL ofacetonitrile and 4.65 g (50 mmol) of aniline at 65° C. The crude productis purified by vacuum flash chromatography (heptane) to give 4.2 g ofthe title compound as a colorless oil in a 72.4% yield.

EXAMPLE 26 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0391] This example shows the use of a two molar excess of aniline, 0.5mole % of cobalt(II) acetate and acetonitrile.

[0392] The procedure of Example 1 is repeated using 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, and 7.84 g (76 mmol) of tert-butylnitrite, 44 mg (0.25 mmol) of cobalt(II) acetate, 120 mL of acetonitrileand 4.65 g (50 mmol) of aniline at 65° C. The crude product is purifiedby vacuum flash chromatography (heptane) to give 3.9 g of the titlecompound as a colorless oil in a 67.2% yield.

EXAMPLE 27 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0393] This example shows the use of a two molar excess of aniline, 0.5mole % of manganese(II) chloride and acetonitrile.

[0394] The procedure of Example 1 is repeated using 3.9 g (25 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, and 7.84 g (76 mmol) of tert-butylnitrite, 31 mg (0.25 mmol) of manganese(II) chloride, 120 mL ofacetonitrile and 4.65 g (50 mmol) of aniline at 70° C. The crude productis purified by vacuum flash chromatography (heptane) to give 3.6 g ofthe title compound as a colorless oil in a 62.1% yield.

EXAMPLE 28 1-Phenoxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

[0395] The procedure of Example 1 is repeated using 5.79 g (0.021 mmol)of 1-oxyl-4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 5.05 g (49 mmol)of tert-butyl nitrite, 12.6 mg (0.125 mmol) of copper(II) fluoride, 120mL of pyridine and 3.91 g (42 mmol) of aniline at 70° C. The crudeproduct obtained is purified by vacuum flash chromatography (heptane) togive 4.10 g of the title compound as a yellowish oil in 55.3% yield. Thestructure is confirmed by mass spectrographic analysis. MS [M+1]354.

EXAMPLE 29 N-Phenoxy-di-tert-butylamine

[0396] The procedure of Example 1 is repeated using 1.80 g (12.5 mmol)of di-tert-butyl nitroxide, 3.09 g (38 mmol) of tert-butyl nitrite, 7.6mg (0.125 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),120 mL of pyridine and 2.30 g (25 mmol) of aniline at 70° C. The crudeproduct obtained is purified by vacuum flash chromatography (heptane) togive 2.21 g of the title compound as a colorless oil in 80.3% yield. Thestructure is confirmed by ¹Hnmr and elemental analysis.

[0397]¹Hnmr (CDCl₃) (300.08 MHz) d 1.26 (s, C(CH₃)₃, 18H), 7.22(overlapping m, 4H), 6.84 (tt, 1H, ³J_(HH′)=6.8 Hz, ⁴J_(HH″)=1.6 Hz).

[0398] Analysis: Calcd for C₁₄H₂₃NO: C, 75.9; H, 10.5; N, 6.3. Found: C,75.4; H, 9.8; N, 6.3.

EXAMPLE 302,4-Bis[N-butyl-N-(1-phenoxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-chloro-s-triazine

[0399] The procedure of Example 1 is repeated using 3.89 g (6.90 mmol)of2,4-bis[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-chloro-s-triazine,3.29 g (32 mmol) of tert-butyl nitrite, 4.2 mg (0.0069 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),120 mL of pyridine and 2.56 g (27.6 mmol) of aniline at 70° C. The crudeproduct obtained is purified by vacuum flash chromatography (heptane) togive 3.0 g of the title compound as an off-white solid in 60.5% yield.

EXAMPLE 312,4-Bis{N-butyl-N-[1-(2,4-dibromophenoxy)-2,2,6,6-tetra-methylpiperidin-4-yl]amino}-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine

[0400] The procedure of Example 1 is repeated using 10 g (13 mmol) of2,4-bis[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine,6.18 g (60 mmol) of tert-butyl nitrite, 7.8 mg (0.013 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),140 mL of pyridine and 13.05 g (52 mmol) of 2,4-dibromoaniline at 85° C.The crude product obtained is purified by vacuum flash chromatography(2% ethyl acetate/heptane) to give 7 g of the title compound as a lightyellow solid in 43.4% yield. The structure is confirmed by ¹Hnmr andelemental analysis.

[0401]¹Hnmr (CDCl₃) (499.84 MHz) d 0.89 (t, CH₃, 12H), 0.97 (t, CH₃,6H), 1.03 (s, CH₃, 12H), 1.44 (s, CH₃, 12H), 1.28 (overlapping m, CH₂,24H), 1.82, 1.60 (overlapping m, CH₂, 8H), 3.35 (overlapping dd, NCH₂,4H), 3.58 (t, NCH₂, 4H), 5.26 (m, NCH, 2H), 7.30 (dd, 2H, ³J_(HH′)=8.79Hz, ⁴J_(HH′)=2.29 Hz), 7.59 (d, 2H, ⁴J_(HH′)=2.32 Hz), 7.48 (d, 2H,³J_(HH′)=8.91 Hz).

[0402] Analysis: Calcd for C₅₇H₉₂Br₄N₈O₂: C, 55.2; H, 7.5; N, 9.0.Found: C, 55.8; H, 7.3; N, 8.7.

EXAMPLE 322,4-Bis[N-butyl-N-(1-phenoxy-2,2,6,6-tetra-methylpiperidin-4-yl)amino]-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine

[0403] The procedure of Example 1 is repeated using 5 g (6.5 mmol) of2,4-bis[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine,3.09 g (30 mmol) of tert-butyl nitrite, 3.9 mg (0.0065 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),120 mL of pyridine and 2.42 g (26 mmol) of aniline at 75° C. The crudeproduct obtained is purified by vacuum flash chromatography (2% ethylacetate/heptane) to give 5 g of the title compound as a reddish oil in83.3% yield. The structure is confirmed by ¹Hnmr and elemental analysis.

[0404]¹Hnmr (CDCl₃) (499.84 MHz) d 0.89 (t, CH₃, 12H), 0.98 (t, CH₃,6H), 1.07 (s, CH₃, 12H), 1.54 (s, CH₃, 12H), 1.27 (overlapping m, CH₂,24H), 1.82, 1.64 (overlapping m, CH₂, 8H), 3.36 (overlapping dd, NCH₂,4H), 3.61 (t, NCH₂, 4H), 5.25 (m, NCH, 2H), 6.87 (dd, 2H, ³J_(HH′)=8.79Hz, ⁴J_(HH′)=2.29 Hz), 7.21 (d, 2H, ⁴J_(HH′)=2.32 Hz), 7.51 (d, 2H,³J_(HH′)=8.91 Hz).

[0405] Analysis: Calcd for C₅₇H₉₆N₈O₂: C, 73.9; H, 10.5; N, 12.1. Found:C, 74.3; H, 10.2; N, 11.9.

EXAMPLE 33 1-(3,5-di-tert-butylphenoxy)-2,2,6,6-tetramethylpiperidine

[0406] The procedure of Example 1 is repeated using 1.50 g (9.6 mmol) of1-oxyl-2,2,6,6-tetramethylpiperidine, 2.38 g (24 mmol) of tert-butylnitrite, 5.8 mg (0.0096 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),90 mL of pyridine and 3.93 g (19.2 mmol) of 3,5-di-tert-butylaniline at70° C. The crude product obtained is purified by vacuum flashchromatography (heptane) to give 2.8 g of the title compound as anoff-white solid in 84.8% yield. The structure is confirmed by ¹Hnmr andelemental analysis.

[0407]¹Hnmr (CDCl₃) (499.84 MHz) 1.43, 1.61 (overlapping m, CH₂ 6H),1.02 (s, CH₃, 6H), 1.24 (s, CH₃, 6H), 1.31 (s, CH₃, 18H), 6.88 (t, CH,1H), 7.03 (d, OCCH, 1H, ⁴J_(HH″)=1.9 Hz).

[0408] Analysis: Calcd for C₂₃H₃₉NO: C, 79.9; H, 11.4; N, 4.1. Found: C,80.0; H, 11.7; N, 4.0.

EXAMPLE 34 1-(Pyridin-3-yloxy)-2,2,6,6-tetramethylpiperidine

[0409] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 3.90 g (38 mmol) of tert-butylnitrite, 7.6 mg (0.0125 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),120 mL of pyridine and 2.35 g (25 mmol) of 3-aminopyridine at 70° C. Thecrude product obtained is purified by vacuum flash chromatography(heptane) to give 1.5 g of the title compound as a colorless oil in50.8% yield. The structure is confirmed by ¹Hnmr and mass spectrographicanalyses.

[0410]¹Hnmr (C₆D₆) (300.08 MHz) 1.07, 1.20, 1.29 (overlapping m, CH₂,6H), 0.89 (s, CH₃, 6H), 1.07 (s, CH₃, 6H), 6.71 (ddd, ³J_(HH′)=8.42 Hz,³J_(HH′)=4.56 Hz, ⁵J_(HH′)=0.61 Hz), 7.26 (ddd,³J_(HH′)=8.37 Hz,⁴J_(HH″)=2.76 Hz, ⁴J_(HH′)=1.34 Hz), 8.22 (dd, ³J_(HH′)=2.37 Hz,⁴J_(HH′)=1.37 Hz), 8.80 (d, ⁴J_(HH′)=2.74 Hz); MS m/z 249.

EXAMPLE 351-(2-Nitro-4-chlorophenoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidine

[0411] The procedure of Example 1 is repeated using 4.31 g (25 mmol) of1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 7.73 g (75 mmol) oftert-butyl nitrite, 25 mg (0.25 mmol) of copper(II) flouride, 70 mL ofpyridine and 5.61 g (32.5 mmol) of 4-chloro-2-nitroaniline at 70° C. Thecrude product obtained is purified by vacuum flash chromatography(70:30/heptane:ethyl acetate) to give 4.28 g of the title compound in84.8% yield as a light yellow solid melting at 124-125.5° C. Thestructure is confirmed by ¹Hnmr and elemental analysis.

[0412]¹Hnmr (CDCl₃) (499.85 MHz) 1.06 (s, 6H), 1.35 (s, 6H), 1.64 (dd,2H), 1.98 (dd, 2H), 4.12 (tt. 1H), 7.43 (dd, 1H), 7.83 (dd, 1H), 7.87(dd, 1H).

[0413] Analysis: Calcd for C₁₅H₂₁ClN₂O₄: C, 54.8; H, 6.4; N, 8.5. Found:C, 54.7; H, 6.2; N, 8.5.

EXAMPLE 36 4,4′-Bis(2,2,6,6-tetramethylpiperidin-1-yloxy)benzophenone

[0414] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 6.19 g (60 mmol) of tert-butylnitrite, 7.6 mg (0.0125 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),80 mL of pyridine and 5.30 g (25 mmol) of 4,4′-diaminobenzophenone at70° C. The crude product obtained is purified by vacuum flashchromatography (1% ethyl acetate in heptane) to give 0.6 g of the titlecompound as a yellow solid in 9.17% yield. The structure is confirmed by¹Hnmr and mass spectrographic analysis.

[0415]¹Hnmr (CDCl₃) (300.08 MHz) 1.39, 1.28, 1.25 (overlapping m, CH₂,12H), 0.97 (s, CH₃, 12H), 1.13 (s, CH₃, 12H), 7.13 (d, 4H, ³J_(HH′)=9.0Hz), 7.86 (d, 4H, ³J_(HH′)=9.0 Hz); MS[M+1]493.

EXAMPLE 37 Di(1-phenoxy-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate

[0416] The procedure of Example 1 is repeated using 23.32 g (240 mmol)of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 30.9 g (300mmol) of tert-butyl nitrite, 35.5 mg (0.059 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),120 mL of pyridine and 22.32 g (240 mmol) of aniline at 70° C. A totalof 10 g of the 47 g of crude product is purified by vacuum flashchromatography (1% ethyl acetate in heptane) to give 4.0 g of the titlecompound as a yellowish solid in 47.9% yield. The structure is confirmedby ¹Hnmr, elemental and mass spectrographic analyses.

[0417]¹Hnmr (C₆D₆) (300.08 MHz) 1.63, 1.73, 1.95 (overlapping m, CH₂,12H), 1.06 (s, CH₃, 12H), 1.34 (s, CH₃, 12H), 2.30 (t, OCOCH₂,³J_(HH′)=7.7 Hz), 5.13 (m, CHOCO, 2H), 7.21 (d, CH, 4H, ³J_(HH′)=6.8Hz), 7.19 (d, CH, 4H, ³J_(HH′)=7.29 Hz), 6.87 (tt, CH, 2H, ³J_(HH′)=6.8Hz, ⁴J_(HH″)=1.6 Hz); MS[M+1] m/z 665.

[0418] Analysis: C₄₀H₆₀N₂O₆: C, 72.3; H, 9.1; N, 4.2. Found: C, 72.3; H,9.3; N, 4.5.

EXAMPLE 38 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0419] This example shows the use of 1 molar excess aniline, pyridineand 0.03 mole % of gold(I) catalyst.

[0420] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 3.09 g (30 mmol) of tert-butylnitrite, 2.9 mg (0.0125 mmol) of gold(I) chloride in a mixture of 80 mLof pyridine and 2.33 g (25 mmol) of aniline at 70° C. The crude productobtained is purified by vacuum flash chromatography (heptane) to give2.58 g of the title compound as a colorless oil in 88.6% yield.

EXAMPLE 39 1-Phenoxy-2,2,6,6-tetramethylpiperidine

[0421] This example shows the use of 2 molar excess aniline, 2 molarpyridine, chlorobenzene and 0.03 mole % of cobalt(II) catalyst.

[0422] The procedure of Example 1 is repeated using 1.95 g (12.5 mmol)of 1-oxyl-2,2,6,6-tetramethylpiperidine, 3.09 g (30 mmol) of tert-butylnitrite, 7.5 mg (0.0125 mmol) of(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),120 mL of chlorobenzene and 2.30 g (25 mmol) of aniline at 70° C. Thecrude product obtained is purified by vacuum flash chromatography(heptane) to give 2.53 g g of the title compound as a colorless oil in86.6% yield.

EXAMPLE 401-(Phthalimid-4-yloxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine

[0423] The procedure of Example 1 is repeated using 4.31 g (25 mmol) of1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 5.16 g (50 mmol) oftert-butyl nitrite, 15 mg (0.025 mmol) of(R,R)-(+)-N,N-bis(3,4-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),125 mL of pyridine and 4.86 g (30 mmol) of 4-aminophthalimide at 75° C.to give the title compound, MS 318.

EXAMPLE 41 1-Phenoxy-3-carboxy-2,2,5,5-tetramethylpyrrolidine

[0424] The title compound is prepared by the procedure of Example 21 bysubstituting 1-oxyl-3-carboxy-2,2,5,5-tetramethylpyrrolidine in place of1-oxyl-2,2,6,6-tetramethylpiperidine.

EXAMPLE 424,4′-Bis[(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxy]diphenylmethane

[0425] The procedure of Example 1 is repeated using 8.61 g (50 mmol) of1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 7.73 g g (75 mmol) oftert-butyl nitrite, 30 mg (0.05 mmol) of(R,R)-(−)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),100 mL of pyridine and 4.96 g (25 mmol) of 4,4′-methylenedianiline in 25mL of pyridine at 70° C. The residue is triturated with 300 mL ofisopropanol and the resultant solid is collected by filtration. Thecrude product obtained is purified by vacuum flash chromatography (10%ethyl acetate/heptane followed by 50% ethyl acetate/heptane) followed byrecrystallization from acetonitrile (15 mL) to give 0.18 g of a lightyellow solid: MS m/z 510.

[0426] The bis(trimethylsilyl)trifluoroacetamide derivatived sample[bis(trimethylsilyl)-derivative of the two hydroxyl substituents] showedthe appropriate molecular ion in the mass spectrum at 654.

EXAMPLE 43

[0427] Molding grade polypropylene is dry blended with test additivesand then melt compounded into pellets. The pelletized fully formulatedresin is then injection molded into test specimens using a Boy 50Mlaboratory model injection molder.

[0428] Test plaques are mounted in metal frames and exposed in an AtlasCi65 Xenon Arc Weather-Ometer with intermittent light/dark cycles andwater spray following ASTM G26 test procedure. Specimens are tested atperiodic intervals for changes in tensile properties. Failure in thistest is determined by the observation of the loss of tensile properties.The longer it takes for the loss in properties to occur, the moreeffective is the stabilizer system.

[0429] The test samples containing the instant compounds of Examples 1,8, 9, 14, 15 and 16 exhibit good light stabilization properties.

[0430] Raw Materials

[0431] Wax samples are supplied by the Candle-Lite Corporation. Thesesamples contain dyes and fragrances.

[0432] The UV absorbers and hindered amine stabilizers are obtained fromthe Ciba Speciality Chemicals Corporation.

[0433] Sample Preparation

[0434] The wax samples obtained from the Candle-Lite Corporation alreadycontain a dye and a fragrance (scent). In these cases, the wax is meltedand the appropriate stabilizer(s) is (are) added and dissolved in themolten wax. The stabilized wax is then poured into five (5) 44 mmdiameter aluminum pans giving five (5) wax disks.

[0435] Sample Exposure

[0436] Triplicate samples of each disk are exposed under a bank of six(6) cool-white fluorescent lamps (40 watts) or under a bank of six (6)UV lamps having a wavelength of 368 nm with the test samples beingtwelve (12) inches (30.48 cm) below the lamps.

[0437] Dye color fade (or color change) is measured by a MacbethColorEye Spectrophotometer with a 6 inch integrating sphere. Theconditions are: 10 degree observer, D65 illuminant and 8 degree viewingangle.

[0438] Initial color measurements are taken using the above parameters.The L, a and b values are calculated using the CIE system from thereflectance values. YI is calculated from the L, a and b values.Subsequent measurements are taken at specified intervals. Delta L, a, band YI values are simply the difference between the initial values andthe values at each interval. Delta(Δ) E is calculated as follows:

[(Delta L)²+(Delta a)²+(Delta b)²]^(½) =Delta E.

EXAMPLE 44 Color Fade of White Scented Candle Wax under Fluorescent LampExposure

[0439] A variety of different stabilizers are evaluated in white scentedcandle wax obtained from the Candle-Lite Corporation under fluorescentlamp exposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after ΔE after ΔE after Sample* (wt %add) 5.9 days 11.8 days 35 days Blank (no add) 42.90 45.50 45.14 A(0.15%) + B (0.15%) 24.48 26.36 27.80 C (0.15%) + D (0.15%) 13.34 15.2618.16 C (0.15%) + E (0.15%) 14.82 22.44 25.86 C (0.15%) + F (0.15%)11.43 13.61 14.64

[0440] These data show that the instant compound of Example 28 protectswhite scented candle from discoloring better than do conventionalstabilizer systems.

EXAMPLE 45 Color Fade of Gray Scented Candle Wax under Fluorescent LampExposure

[0441] A variety of different stabilizers are evaluated in gray scentedcandle wax obtained from the Candle-Lite Corporation under fluorescentlamp exposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after ΔE after ΔE after Sample* (wt %add) 4.9 days 15.5 days 33.9 days Blank (no add) 9.66 14.07 16.01 A(0.15%) + B (0.15%) 0.62 0.90 1.69 C (0.15%) + D (0.15%) 1.04 1.82 3.16C (0.15%) + E (0.15%) 1.74 2.63 4.46 C (0.15%) + F (0.15%) 1.75 2.684.89

[0442] These data show that the instant compound of Example 1 and 28protect gray scented candle from discoloring nearly as well as doconventional stabilizer systems.

EXAMPLE 46 Color Fade of Pink Potpouri Scented Candle Wax underFluorescent Lamp Exposure

[0443] A number of stabilizers are evaluated in pink potpouri scentedcandle wax obtained from the Candle-Lite Corporation under fluorescentlamp exposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after ΔE after ΔE after Sample* (wt %add) 8.9 days 11.8 days 22.3 days Blank (no add) 8.10 10.22 12.12 A(0.15%) + B (0.15%) 1.25 1.01 1.17 C (0.15%) + D (0.15%) 1.84 2.73 3.20C (0.15%) + E (0.15%) 6.52 8.64 10.62 C (0.15%) + F (0.15%) 3.32 5.096.97

[0444] These data show that the instant compounds of Examples 1 and 28provide the pink potpouri scented candle some protection fromdiscoloring.

EXAMPLE 47 Color Fade of White Scented Candle Wax under UV Lamp Exposure

[0445] A variety of different stabilizers are evaluated in white scentedcandle wax obtained from the Candle-Lite Corporation under UV lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after ΔE after ΔE after Sample* (wt %add) 4 days 10.1 days 33 days Blank (no add) 27.56 32.71 34.68 A(0.15%) + B (0.15%) 18.66 23.57 25.09 C (0.15%) + D (0.15%) 5.16 6.6810.27 C (0.15%) + E (0.15%) 10.44 16.62 23.03 C (0.15%) + F (0.15%) 5.779.39 13.16

[0446] These data show that the instant compound of Example 28 protectswhite scented candle from discoloring far better than do someconventional stabilizer systems.

EXAMPLE 48 Color Fade of Gray Scented Candle Wax under UV Lamp Exposure

[0447] A variety of different stabilizers are evaluated in gray scentedcandle wax obtained from the Candle-Lite Corporation under UV lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after ΔE after ΔE after Sample* (wt %add) 2.8 days 8.9 days 22.6 days Blank (no add) 22.20 28.98 30.07 A(0.15%) + B (0.15%) 1.16 2.73 3.83 C (0.15%) + D (0.15%) 1.70 3.47 5.11C (0.15%) + E (0.15%) 1.41 3.13 5.36 C (0.15%) + F (0.15%) 1.57 3.275.38

[0448] These data show that the instant compounds of Examples 1 and 28protect gray scented candle from discoloring as well as do someconventional stabilizer systems.

EXAMPLE 49 Color Fade of Pink Potpouri Scented Candle Wax under UV LampExposure

[0449] A number of stabilizer compounds are evaluated in pink potpouriscented candle wax obtained from the Candle-Lite Corporation underfluorescent lamp exposure. The ΔE values represent the change in colorafter the indicated days of exposure. A low ΔE value indicates lesschange in color and is highly desired. ΔE after ΔE after ΔE afterSample* (wt % add) 7.6 days 18.4 days 36.7 days Blank (no add) 16.1617.47 20.27 A (0.15%) + B (0.15%) 3.18 3.60 4.35 C (0.15%) + D (0.15%)5.12 2.84 3.44 C (0.15%) + E (0.15%) 6.35 7.76 11.07 C (0.15%) + F(0.15%) 5.83 7.05 9.26

[0450] These data show that the instant compounds of Examples 1 and 28provide the pink potpouri scented candle with some protection fromdiscoloring.

What is claimed is:
 1. A process for preparing a sterically hinderedN-aryloxyamine of formula I, II, III, IV, V or VI

which comprises reacting a sterically hindered nitroxyl compound offormula VII, VIII, IX, X or XI

with a diazonium salt of an aromatic amine of formula XII, XIII or XIV

in the presence of a transition-metal catalyst wherein X is —CH₂—, —O—,—S— or —NR₈— where R₈ is hydrogen or alkyl of 1 to 12 carbon atoms, R₆and R₇ are independently alkyl of 1 to 8 carbon atoms, or R₆ and R₇together are tetramethylene or pentamethylene,

E₂ is alkylene of 2 to 12 carbon atoms, G is chloro or—N(2-ethylhexyl)₂, G₁ is —CH₂—, —CO— or —O—, R is hydrogen, alkyl of 1to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms, hydroxyl, carboxyl, amino, alkylamino of 1 to 18 carbonatoms, dialkylamino of 2 to 36 carbon atoms, oxo, alkylthio of 1 to 18carbon atoms, alkoxy of 1 to 18 carbon atoms, aryloxy of 7 to 15 carbonatoms, benzoyloxy, alkylcarbonyloxy of 2 to 18 carbon atoms oralkylcarbonylamino of 2 to 18 carbon atoms, and R₁ to R₅ areindependently hydrogen, halogen, nitro, cyano, alkyl of 1 to 18 carbonatoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms,hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, alkoxy of 1 to 18carbon atoms, aryloxy of 7 to 15 carbon atoms, alkylcarbonyloxy of 1 to18 carbon atoms, alkylsulfonyl of 1 to 18 carbon atoms, arylsulfonyl of6 to 15 carbon atoms, sulfo or —P(O)(OH)₂ or —P(O)(OR₆)₂, or any twovicinal substituents connected together to form a mono or polycyclicring, so that formula VII can represent inter alia 1-naphthylamine or2-naphthylamine; or any two vicinal carboxyl groups can be joined toform an imide; or

 where R, R₆ and R₇ are as defined above.
 2. A process according toclaim 1 wherein X is methylene.
 3. A process according to claim 1wherein R is hydrogen, hydroxyl, oxo or acetamido.
 4. A processaccording to claim 1 wherein R₁ to R₅ are each hydrogen; or R₁ is nitro,R₃ is chloro or trifluoromethyl, and R₂, R₄ and R₅ are hydrogen; or R₁and R₃ are bromo, and R₂, R₄ and R₅ are hydrogen.
 5. A process accordingto claim 1 wherein R₆ and R₇ are each methyl.
 6. A process according toclaim 1 wherein R₁ and R₃ are each bromo or chloro.
 7. A processaccording to claim 1 wherein the N-aryloxyamine is (a)1-phenoxy-2,2,6,6-tetramethylpiperidine; (b)1-phenoxy-2,2,6,6-tetramethyl-4-hydroxypiperidine; (c)1-(2-nitro-4-trifluoromethylphenoxy)-2,2,6,6-tetramethylpiperidine; (d)1-(2-nitro-4-chlorophenoxy)-2,2,6,6-tetramethylpiperidine; (e)1-(2,4-dibromophenoxy)-2,2,6,6-tetramethylpiperidine; (f)1-(2,4-dibromophenoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine; (g)1-(2,4-dibromophenoxy)-4-acetamido-2,2,6,6-tetramethylpiperidine; (h)1-(2,4-dibromophenoxy)-4-oxo-2,2,6,6-tetramethylpiperidine; (i)1-(2-naphthyloxy)-2,2,6,6-tetramethylpiperidine; (j)1-(4-benzoylphenoxy)-2,2,6,6-tetramethylpiperidine; (k)1-phenoxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine; (l)N-phenoxy-di-tert-butylamine; (m)2,4-bis[N-butyl-N-(1-phenoxy-2,2,6,6-tetra-methylpiperidin-4-yl)amino]-6-chloro-s-triazine;(n)2,4-bis{N-butyl-N-[1-(2,4-dibromophenoxy)-2,2,6,6-tetramethylpiperidin-4-yl]amino}-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine;(o)2,4-bis[N-butyl-N-(1-phenoxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine;(p) 1-(3,5-di-tert-butylphenoxy)-2,2,6,6-tetramethylpiperidine; (q)1-(pyridin-3-yloxy)-2,2,6,6-tetramethylpiperidine; (r)1-(2-nitro-4-chlorophenoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidine; (s)4,4′-bis(2,2,6,6-tetramethylpiperidin-1-yloxy)benzophenone; (t)di(1-phenoxy-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate; (u)1-phenoxy-3-carboxyl-2,2,5,5-tetramethylpyrrolidine; (v)4,4′-bis[(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxy]diphenylmethane;or (w) 1-(phthalimid-4-yloxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine.8. A process according to claim 1 wherein the diazonium salt of thearomatic amine of formula VII is prepared by reaction with an alkylnitrite.
 9. A process according to claim 8 wherein the alkyl nitrite istert-butyl nitrite.
 10. A process according to claim 1 wherein reactionis carried out in acetonitrile as solvent at a temperature of 0 to 100°C.
 11. A process according to claim 10 wherein the temperature isbetween 20 and 70° C.
 12. A process according to claim 1 wherein thereaction is carried out with pyridine present as a reaction component oras the solvent.
 13. A process according to claim 1 wherein thetransition metal is a metal of Group 4, 5, 6, 7, 8, 9 or 10 of theperiodic table.
 14. A process according to claim 13 wherein thetransition metal is copper(I), copper(II), cobalt(II), manganese(II),titanium(III), iron(II), iron(III), cobalt(II), nickel(II), gold(I) orchromium(III).
 15. A process according to claim 1 wherein the process iscarried out in the presence of 0.1 mole % to stoichiometric quantitiesof the transition metal catalyst.
 16. A process according to claim 1wherein the the transition metal catalyst is copper(I) or copper(II).17. A process according to claim 16 wherein the transition metalcatalyst is copper(II) fluoride.
 18. A process according to claim 13wherein the transition metal catalyst is gold(I) chloride.
 19. A processaccording to claim 13 wherein the transition metal catalyst is(S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II),N,N-bis(salicylidene)ethylenediaminocobalt(II) or(R,R)-(−)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II).20. A compound which is (i)1-(2-nitro-4-trifluoromethylphenoxy)-2,2,6,6-tetramethylpiperidine; (ii)1-(2-nitro-4-chlorophenoxy)-2,2,6,6-tetramethylpiperidine; (iii)1-(2,4-dibromophenoxy)-2,2,6,6-tetramethylpiperidine; (iv)1-(2,4-dibromophenoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine; (v)1-(2,4-dibromophenoxy)-4-acetamido-2,2,6,6-tetramethylpiperidine; (vi)1-(2,4-dibromophenoxy)-4-oxo-2,2,6,6-tetramethylpiperidine; (vii)1-(2-naphthyloxy)-2,2,6,6-tetramethylpiperidine; (viii)1-(4-benzoylphenoxy)-2,2,6,6-tetramethylpiperidine; (ix)1-phenoxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine; (x)N-phenoxy-di-tert-butylamine; (xi)2,4-bis[N-butyl-N-(1-phenoxy-2,2,6,6-tetra-methylpiperidin-4-yl)amino]-6-chloro-s-triazine;(xii)2,4-bis{N-butyl-N-[1-(2,4-dibromophenoxy)-2,2,6,6-tetramethylpiperidin-4-yl]amino}-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine;(xiii)2,4-bis[N-butyl-N-(1-phenoxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-[N,N-bis(2-ethylhexyl)amino]-s-triazine;(xiv) 1-(3,5-di-tert-butylphenoxy)-2,2,6,6-tetramethylpiperidine; (xv)1-(pyridin-3-yloxy)-2,2,6,6-tetramethylpiperidine; (xvi)1-(2-nitro-4-chlorophenoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidine;(xvii) 4,4′-bis(2,2,6,6-tetramethylpiperidin-1-yloxy)benzophenone;(xviii) di(1-phenoxy-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate; (xix)1-phenoxy-3-carboxyl-2,2,5,5-tetramethylpyrrolidine; (xx)4,4′-bis[(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxy]diphenylmethane,or (xxi) 1-(phthalimid-4-yloxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine.21. A process according to claim 1 wherein the diazonium salt of thearomatic amine of formula VII is prepared by reaction of the amine withan alkali metal nitrite and an aqueous mineral acid.
 22. A compositionstabilized which comprises (a) an organic material subject todegradation by heat, light or oxygen, and (b) an effective stabilizingamount of a compound of formula I, II, III, IV, V or VI as described inclaim
 1. 23. A composition which comprises (a) candle wax which is whiteand scented, white and unscented, dyed and scented, dyed and unscented,dipped and scented or dipped and unscented, and (b) an effectivestabilizing amount of a compound of formula I, II, III, IV, V or VI

wherein X is —CH₂—, —O—, —S— or —NR₈— where R₈ is hydrogen or alkyl of 1to 12 carbon atoms, R₆ and R₇ are independently alkyl of 1 to 8 carbonatoms, or R₆ and R₇ together are tetramethylene or pentamethylene,

E₂ is alkylene of 2 to 12 carbon atoms, G is chloro or—N(2-ethylhexyl)₂, G₁ is —CH₂—, —CO— or —O—, R is hydrogen, alkyl of 1to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms, hydroxyl, carboxyl, amino, alkylamino of 1 to 18 carbonatoms, dialkylamino of 2 to 36 carbon atoms, oxo, alkylthio of 1 to 18carbon atoms, alkoxy of 1 to 18 carbon atoms, aryloxy of 7 to 15 carbonatoms, benzoyloxy, alkylcarbonyloxy of 2 to 18 carbon atoms oralkylcarbonylamino of 2 to 18 carbon atoms, and R₁ to R₅ areindependently hydrogen, halogen, nitro, cyano, alkyl of 1 to 18 carbonatoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms,hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, alkoxy of 1 to 18carbon atoms, aryloxy of 7 to 15 carbon atoms, alkylcarbonyloxy of 1 to18 carbon atoms, alkylsulfonyl of 1 to 18 carbon atoms, arylsulfonyl of6 to 15 carbon atoms, sulfo or —P(O)(OH)₂ or —P(O)(OR₆)₂, or any twovicinal substituents connected together to form a mono or polycyclicring, so that formula VII can represent inter alia 1-naphthylamine or2-naphthylamine; or any two vicinal carboxyl groups can be joined toform an imide; or

 where R, R₆ and R₇ are as defined above.
 24. A composition according toclaim 23 which additionally contains an effective stabilizing amount ofa UV absorber.